CN110336036B - Semispherical hollow titanium dioxide/carbon particle/polyaniline sulfur-loaded composite material and preparation method thereof, lithium-sulfur battery positive electrode and battery - Google Patents

Semispherical hollow titanium dioxide/carbon particle/polyaniline sulfur-loaded composite material and preparation method thereof, lithium-sulfur battery positive electrode and battery Download PDF

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CN110336036B
CN110336036B CN201910646904.4A CN201910646904A CN110336036B CN 110336036 B CN110336036 B CN 110336036B CN 201910646904 A CN201910646904 A CN 201910646904A CN 110336036 B CN110336036 B CN 110336036B
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titanium dioxide
sulfur
polyaniline
carbon
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刘金云
程孟莹
韩阗俐
丁颖艺
吴勇
李金金
翟慕衡
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Anhui Normal University
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Abstract

The invention discloses a hemispherical hollow titanium dioxide/carbon particle/polyaniline sulfur-loaded composite material, a preparation method thereof, a lithium-sulfur battery positive electrode and a battery. Firstly, titanium dioxide is obtained by a hydrothermal method, then dopamine is used as a carbon source to wrap a carbon layer, then polyaniline grows in an in-situ polymerization manner, finally sulfur particles are loaded in a sulfur smoking manner, and finally the titanium dioxide/carbon particles/polyaniline sulfur-loaded hemispherical hollow composite material is obtained. The material is applied to the positive electrode material of the lithium-sulfur battery, and has good cycling stability and higher specific capacity. Compared with the prior art, the material prepared by the invention is in a hemispherical hollow shape, has a large specific surface area of a hemispherical hollow structure, can load more sulfur particles, is beneficial to electron transmission, relieves volume expansion in the charge-discharge process, and improves the battery performance. And the experimental process is simple, and the raw materials are cheap and easy to obtain.

Description

Semispherical hollow titanium dioxide/carbon particle/polyaniline sulfur-loaded composite material and preparation method thereof, lithium-sulfur battery positive electrode and battery
Technical Field
The invention belongs to the technical field of new energy materials, and particularly relates to a hemispherical hollow titanium dioxide/carbon particle/polyaniline sulfur-loaded composite material, a preparation method thereof, a lithium-sulfur battery positive electrode and a battery.
Background
Due to environmental pollution and exhaustion of fossil fuels, the storage amount of non-renewable energy resources is reduced day by day, the climate environment is severe day by day, and ecosystems are fragile and weak, and the requirements of clean and renewable energy resources such as solar energy, wind energy and the like are more and more urgently developed, and secondary batteries with high energy density, long cycle life, high safety, environmental protection and low cost have great significance in the field of new energy resources.
The lithium-sulfur battery is a lithium battery with sulfur element as the positive electrode and metallic lithium as the negative electrode, and the theoretical specific energy of the lithium-sulfur battery is as high as 2600Wh/kg and higher than the theoretical specific capacity (1675mAh/g), which is far higher than that of the lithium ion battery commercialized at present. In recent years, lithium-sulfur batteries have become a new hot research trend due to their advantages of wide sources, low cost and high biocompatibility. And because the electrode material of the lithium-sulfur battery is cheap in elemental sulfur, rich in resources and environment-friendly, the lithium-sulfur battery system has high commercial value.
However, three challenges inherent in lithium sulfur batteries have been inhibiting their further development, namely elemental sulfur and discharge products (Li)2S), severe volume expansion during charging and discharging, and dissolution of the intermediate polysulfide in the electrolyte, which lead to low sulfur utilization, poor cycle performance, fast capacity fade, and poor rate performance in batteries.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a semispherical hollow titanium dioxide/carbon particle/polyaniline sulfur-loaded composite material. The reasonable hemispherical hollow structure has a large specific surface area, is favorable for electron transmission, and can load more active substances.
The invention also aims to provide a preparation method of the semi-spherical hollow titanium dioxide/carbon particle/polyaniline sulfur-loaded composite material, which comprises the steps of preparing titanium dioxide by using low-cost raw materials, wrapping carbon by using dopamine as a carbon source, growing polyaniline in an ice bath environment to obtain a titanium dioxide/carbon particle/polyaniline nano material, and then loading sulfur to obtain the lithium-sulfur battery cathode material. The preparation process is simple, the yield is high, and the cost is low.
The invention also aims to provide a lithium-sulfur battery positive electrode which is made of the hemispherical hollow titanium dioxide/carbon particle/polyaniline sulfur-loaded composite material.
A final object of the present invention is to provide a battery comprising the above-mentioned lithium sulfur battery positive electrode.
The specific technical scheme of the invention is as follows:
a preparation method of a semispherical hollow titanium dioxide/carbon particle/polyaniline sulfur-loaded composite material comprises the following steps:
1) uniformly mixing absolute ethyl alcohol and isopropanol, adding tetrabutyl titanate, uniformly mixing, and carrying out hydrothermal reaction to obtain a titanium dioxide material;
2) dispersing the titanium dioxide material prepared in the step 1) in water, adding trihydroxymethyl aminomethane, adding dopamine hydrochloride, reacting, and obtaining a titanium dioxide/carbon nano material after the reaction is finished;
3) roasting the titanium dioxide/carbon nano material prepared in the step 2) in a nitrogen atmosphere, and naturally cooling to room temperature to prepare titanium dioxide/carbon particles;
4) dispersing the titanium dioxide/carbon particles prepared in the step 3) in a sulfuric acid solution under an ice bath condition, adding aniline, uniformly stirring, and then adding ammonium persulfate to react to obtain hemispherical hollow titanium dioxide/carbon particles/polyaniline;
5) uniformly mixing the hemispherical hollow titanium dioxide/carbon particles/polyaniline prepared in the step 4) with sulfur powder, and fumigating sulfur in an argon atmosphere to obtain the hemispherical hollow titanium dioxide/carbon particles/polyaniline sulfur-loaded composite material.
In the step 1), the volume ratio of the absolute ethyl alcohol, the isopropanol and the tetrabutyl titanate is (10-30): (10-20): (0.1 to 1.0);
in the step 1), the hydrothermal reaction is carried out for 4-12 h at 150-200 ℃, preferably for 5-8 h at 155-190 ℃.
In the step 1), after the reaction is finished, the method further comprises the steps of cooling the product to room temperature, centrifuging, washing and drying.
In the step 2), the mass ratio of the titanium dioxide material, the trihydroxymethyl aminomethane and the dopamine hydrochloride is 1: (1-8): (0.2 to 0.5), preferably 1: (1.5-7.5): (0.225-0.45).
In the step 2), the concentration of the titanium dioxide material in water is 2-6 g/L, preferably 3-5 g/L.
The step 2) also comprises the following steps: and adding the tris (hydroxymethyl) aminomethane to adjust the pH of the system to 6.5-10, preferably 8-9.5.
In the step 2), the reaction time is 18-30 h, preferably 20-26 h.
In the step 2), after the reaction is finished, the method also comprises the steps of cooling the product to room temperature, centrifuging, washing and drying.
In the step 3), roasting is carried out for 2-8 h at 500-800 ℃ and for 3-6h at 550-750 ℃.
In the step 4), the using amount ratio of the titanium dioxide/carbon particles to the aniline to the ammonium persulfate is 1 g: (0.15-3.0) mL (2-4) g; the concentration of the titanium dioxide/carbon particles in sulfuric acid is 2-6 g/L; the concentration of the sulfuric acid is 0.3-1 mol/L, preferably 0.5-0.8 mol/L.
In the step (4), the reaction time is 6-18 h, preferably 8-15 h.
In the step 4), after the reaction is finished, the method also comprises the steps of centrifuging, washing and drying the product; the drying is vacuum drying, the vacuum drying condition is that the drying is carried out for 4-18 h at the temperature of 45-85 ℃, and the drying is preferably carried out for 6-8 h at the temperature of 55-70 ℃.
In the step 5), the mass ratio of the hemispherical hollow titanium dioxide/carbon particles/polyaniline to the sulfur powder is 1: 1-5; the sulfuring condition is 140-180 ℃ sulfuring for 12-18 h, preferably 145-175 ℃ sulfuring for 14-16 h.
According to the preparation method, the size of the prepared hemispherical hollow titanium dioxide/carbon particle/polyaniline sulfur-loaded composite material is 2-4 microns.
The invention provides application of the semispherical hollow titanium dioxide/carbon particle/polyaniline sulfur-loaded composite material prepared by the preparation method as a lithium ion battery anode material.
The invention provides a lithium-sulfur battery anode which is prepared from the hemispherical hollow titanium dioxide/carbon particle/polyaniline sulfur-loaded composite material prepared by the preparation method.
The battery provided by the invention comprises the lithium-sulfur battery positive electrode and has good cycle performance.
In order to improve the electrochemical performance of the lithium-sulfur battery, the invention discloses a composite material with a hemispherical hollow shape. The designed hemispherical hollow composite material has a large specific surface area, is favorable for electron transmission, and can load more active substances. The generation of the conductive polymer polyaniline can improve the overall conductivity of the sulfur anode, and can inhibit the dissolution of polysulfide to a certain extent, the hollow shape also plays a role in buffering because polysulfide sulfur chains form polysulfide salt compounds, so that the problem of volume expansion in the charge-discharge process is reduced, the loss of active mass is reduced, and the shuttle of polysulfide is inhibited, thereby improving the electrochemical performance of the anode.
According to the invention, anhydrous ethanol and isopropanol are mixed, tetrabutyl titanate is subjected to ester exchange to obtain titanium dioxide by a hydrothermal method, the volume ratio of the anhydrous ethanol to the isopropanol and the dosage ratio of the tetrabutyl titanate are improved, and the hemispherical hollow titanium dioxide with the optimal morphology and the optimal size is obtained by improving the temperature and the reaction time; dopamine is used as a carbon source, a carbon layer is wrapped on titanium dioxide, polyaniline grows through in-situ polymerization, and sulfur particles are loaded in a sulfur smoking mode to finally obtain the carbon-sulfur-loaded hemispherical hollow composite material. The hemispherical hollow structure is beneficial to sulfur compounding, and carbon can increase the surface roughness of titanium dioxide and is beneficial to the growth of polyaniline. Polyaniline can improve the conductivity of the sulfur anode, and the burr-shaped structure provides a larger specific surface area for later sulfur loading, so that high sulfur loading is obtained. The material is applied to the positive electrode material of the lithium-sulfur battery, and has good cycling stability and high specific capacity.
Compared with the prior art, the titanium dioxide/carbon/polyaniline material is in a hemispherical hollow shape, the specific surface area of the hemispherical hollow structure is large, more sulfur particles can be loaded, the hemispherical hollow structure is favorable for electron transmission, the volume expansion in the charge-discharge process is relieved, and the battery performance is improved. And the experimental process is simple, and the raw materials are cheap and easy to obtain.
Drawings
FIG. 1 is an SEM image of a titania material prepared by step 1) of example 3;
FIG. 2 is an SEM image of the titania/carbon nanomaterial prepared by step 2) of example 3;
FIG. 3 is an SEM photograph of hemispherical hollow titanium dioxide/carbon particles/polyaniline prepared in step 4) of example 3;
fig. 4 is an SEM image of the hemispheric hollow titanium dioxide/carbon particle/polyaniline sulfur-loaded composite material prepared in example 3.
Fig. 5 is a TEM image of a hemispherical hollow titanium dioxide/carbon particle/polyaniline sulfur-loaded composite prepared in example 3.
FIG. 6 is a Mapping chart of a hemispherical hollow titanium dioxide/carbon particle/polyaniline sulfur-loaded composite prepared in example 3;
fig. 7 is an XRD chart of the synthesis process of the hemispheric hollow titanium dioxide/carbon particles/polyaniline sulfur-loaded composite prepared in example 3.
Fig. 8 is an XPS plot of the hemispherical hollow titanium dioxide/carbon particle/polyaniline sulfur-loaded composite prepared in example 3.
Fig. 9 is a graph showing the cycle stability of the hemispheric hollow titanium dioxide/carbon particles/polyaniline sulfur-loaded composite material prepared in example 3 as a lithium sulfur battery at a current density of 0.1C.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
A preparation method of a semispherical hollow titanium dioxide/carbon particle/polyaniline sulfur-loaded composite material comprises the following steps:
1) a hydrothermal process: 10mL of absolute ethanol and 20mL of isopropanol were mixed with stirring. Adding 0.2mL of tetrabutyl titanate, stirring for 10min, putting the mixed solution into an oven, reacting for 12 hours at a constant temperature of 150 ℃, collecting, centrifuging and cleaning precipitates after the reaction is finished, and performing vacuum drying for 18 hours at 40 ℃ to obtain a titanium dioxide material;
2) a compounding procedure: adding 0.2g of the titanium dioxide material prepared in the step 1) into 50mL of deionized water, adding 0.3g of Tris (hydroxymethyl) aminomethane (Tris), adding hydrochloric acid to adjust the pH value to 6.5, adding 45mg of dopamine hydrochloride, reacting for 18 hours, taking out a product after the reaction is finished, centrifuging, alternately cleaning with deionized water and ethanol, and drying in vacuum at 40 ℃ for 20 hours to obtain the titanium dioxide/carbon nano material.
3) A roasting process: roasting the titanium dioxide/carbon nano material prepared in the step 3) for 3 hours at 500 ℃ in a nitrogen atmosphere, and naturally cooling to room temperature to obtain titanium dioxide/carbon particles.
4) A growth procedure: weighing 0.2g of titanium dioxide/carbon particles prepared in the step 3), dispersing in 40mL of 0.3 mol/L sulfuric acid solution, adding 0.3mL of aniline, stirring in an ice bath environment, adding 0.4g of ammonium persulfate, reacting for 6 hours, centrifuging, cleaning, and vacuum-drying at 45 ℃ for 18 hours to obtain the hemispherical hollow titanium dioxide/carbon particles/polyaniline.
5) A sulfuration procedure: uniformly mixing 0.5g of hemispherical hollow titanium dioxide/carbon particles/polyaniline and 0.5g of sulfur powder, putting the mixture into a polytetrafluoroethylene plastic bottle, filling argon into the bottle, keeping the temperature at 120 ℃ for 18 hours, and naturally cooling to obtain the hemispherical hollow titanium dioxide/carbon particles/polyaniline sulfur-loaded composite material.
Example 2
A preparation method of a semispherical hollow titanium dioxide/carbon particle/polyaniline sulfur-loaded composite material comprises the following steps:
1) a hydrothermal process: stirring and mixing 15mL of absolute ethanol and 20mL of isopropanol uniformly, adding 0.4mL of tetrabutyl titanate, stirring for 10min, putting the mixed solution into an oven, reacting for 10 hours at the constant temperature of 160 ℃, collecting, centrifuging and cleaning precipitates after the reaction is finished, and drying for 16 hours in vacuum at the temperature of 50 ℃ to obtain a titanium dioxide material;
2) a compounding procedure: dispersing 0.2g of the titanium dioxide material prepared in the step 1) in 50mL of deionized water, adding 0.8g of Tris (hydroxymethyl) aminomethane (Tris), adding hydrochloric acid to adjust the pH value to 7.5, adding 55mg of dopamine hydrochloride, reacting for 22 hours, taking out a product after the reaction is finished, centrifuging, alternately cleaning with deionized water and ethanol, and drying in vacuum at 55 ℃ for 16 hours to obtain a titanium dioxide/carbon nano material;
3) a roasting process: roasting the titanium dioxide/carbon nano material prepared in the step 2) at 550 ℃ for 3 hours in a nitrogen atmosphere, and naturally cooling to room temperature to prepare titanium dioxide/carbon particles;
4) a growth procedure: weighing 0.2g of titanium dioxide/carbon particles prepared in the step 3), dispersing the titanium dioxide/carbon particles in 50mL of 0.4 mol/L sulfuric acid, adding 0.4mL of aniline, stirring the mixture in an ice bath environment, adding 0.5g of ammonium persulfate, reacting the mixture for 10 hours, centrifuging and cleaning the mixture, and performing vacuum drying at 55 ℃ for 16 hours to obtain hemispherical hollow titanium dioxide/carbon particles/polyaniline;
5) a sulfuration procedure: uniformly mixing 1.0g of hemispherical hollow titanium dioxide/carbon particles/polyaniline and 3.0g of sulfur powder, putting the mixture into a polytetrafluoroethylene plastic bottle, filling argon into the bottle, keeping the temperature at 135 ℃ for 16 hours, and naturally cooling to obtain the hemispherical hollow titanium dioxide/carbon particles/polyaniline sulfur-loaded composite material.
Example 3
A preparation method of a semispherical hollow titanium dioxide/carbon particle/polyaniline sulfur-loaded composite material comprises the following steps:
1) a hydrothermal process: 20mL of absolute ethyl alcohol and 10mL of isopropanol are uniformly stirred and mixed, 0.5mL of tetrabutyl titanate is added and stirred for 10min, the mixed solution is placed into a drying oven and reacts at the constant temperature of 180 ℃ for 8 hours, after the reaction is finished, precipitates are collected, centrifuged and cleaned, and vacuum drying is carried out at 60 ℃ for 12 hours to obtain a titanium dioxide material, wherein an SEM (scanning electron microscope) of the titanium dioxide material is shown in figure 1 and is in a hemispherical hollow shape with a smooth surface and a particle size of 2 microns;
2) a compounding procedure: dispersing 0.2g of the titanium dioxide material prepared in the step 1) in 50mL of deionized water, adding 1.2g of Tris (hydroxymethyl) aminomethane (Tris), adding hydrochloric acid to adjust the pH value to 8.5, adding 60mg of dopamine hydrochloride, reacting for 24 hours, after the reaction is finished, taking out a product, centrifuging, alternately cleaning with deionized water and ethanol, and drying in vacuum at 60 ℃ for 12 hours to obtain the titanium dioxide/carbon nano material, wherein an SEM (scanning electron microscope) is shown in figure 2, and the SEM is a hemispherical hollow structure with a slightly rough surface and a particle size of 2-2.5 mu m.
3) A roasting process: roasting the titanium dioxide/carbon nano material prepared in the step 2) for 4 hours at 600 ℃ in a nitrogen atmosphere, and naturally cooling to room temperature to obtain titanium dioxide/carbon particles.
4) A growth procedure: weighing 0.2g of titanium dioxide/carbon particles prepared in the step 3), dispersing the titanium dioxide/carbon particles in 60mL of 0.5 mol/L sulfuric acid, adding 0.45mL of aniline, stirring in an ice bath environment, dissolving 0.6g of ammonium persulfate in 40mL of sulfuric acid, reacting for 12 hours, centrifuging, cleaning, and vacuum drying at 60 ℃ for 14 hours to obtain hemispherical hollow titanium dioxide/carbon particles/polyaniline, wherein an SEM of the hemispherical hollow titanium dioxide/carbon particles/polyaniline is shown in figure 3, and the hemispherical hollow titanium dioxide/carbon particles/polyaniline is a hemispherical hollow titanium dioxide/carbon particles with burr-shaped polyaniline growing on the surface and the particle size of 2.2-2.7 microns.
5) A sulfuration procedure: 1.0g of hemispherical hollow titanium dioxide/carbon particles/polyaniline and 2.0g of sulfur powder are uniformly mixed and put into a polytetrafluoroethylene plastic bottle, the bottle is filled with argon, the temperature is kept at 155 ℃ for 15 hours, and the bottle is naturally cooled to obtain the hemispherical hollow titanium dioxide/carbon particles/polyaniline sulfur-loaded composite material, wherein SEM and TEM are respectively shown in figures 4 and 5, and the hemispherical hollow structure and burr shape can be seen to be kept complete.
FIG. 6 is a mapping chart of the product of this example. Fig. 7 is an XRD chart of the product obtained in each step of this example, fig. 8 is an XPS chart of the semispherical hollow titanium dioxide/carbon particle/polyaniline sulfur-loaded composite material in this example, and it can be seen from fig. 4 and 5 that the semispherical hollow titanium dioxide/carbon particle/polyaniline sulfur-loaded composite material was successfully prepared in this example.
Example 4
A preparation method of a semispherical hollow titanium dioxide/carbon particle/polyaniline sulfur-loaded composite material comprises the following steps:
1) a hydrothermal process: 20mL of absolute ethyl alcohol and 15mL of isopropanol are stirred and mixed uniformly, 0.7mL of tetrabutyl titanate is added and stirred for 10min, the mixed solution is placed into a drying oven to react for 10 hours at the constant temperature of 180 ℃, after the reaction is finished, the precipitate is collected, centrifuged and cleaned, and is dried for 8 hours in vacuum at 70 ℃ to obtain a titanium dioxide material;
2) a compounding procedure: dispersing 0.2g of the titanium dioxide material prepared in the step 1) in 50mL of deionized water, adding 1.4g of Tris (hydroxymethyl) aminomethane (Tris), adding hydrochloric acid to adjust the pH value to 9, adding 70mg of dopamine hydrochloride, reacting for 26 hours, taking out a product after the reaction is finished, centrifuging, alternately cleaning with deionized water and ethanol, and drying in vacuum at 70 ℃ for 8 hours to obtain a titanium dioxide/carbon nano material;
3) a roasting process: roasting the titanium dioxide/carbon nano material prepared in the step 2) for 6 hours at 700 ℃ in a nitrogen atmosphere, and naturally cooling to room temperature to prepare titanium dioxide/carbon particles;
4) a growth procedure: weighing 0.2g of titanium dioxide/carbon particles prepared in the step 3), dispersing the titanium dioxide/carbon particles in 70mL of 0.7 mol/L sulfuric acid, adding 0.55mL of aniline, stirring in an ice bath environment, dissolving 0.75g of ammonium persulfate in 40mL of sulfuric acid, reacting for 16h, centrifuging, cleaning, and vacuum-drying at 80 ℃ for 8h to obtain hemispherical hollow titanium dioxide/carbon particles/polyaniline;
5) a sulfuration procedure: uniformly mixing 1.0g of hemispherical hollow titanium dioxide/carbon particles/polyaniline and 4.0g of sulfur powder, putting the mixture into a polytetrafluoroethylene plastic bottle, filling argon into the bottle, keeping the temperature at 170 ℃ for 10 hours, and naturally cooling to obtain the hemispherical hollow titanium dioxide/carbon particles/polyaniline sulfur-loaded composite material.
Example 5
A preparation method of a semispherical hollow titanium dioxide/carbon/polyaniline sulfur-loaded composite material comprises the following steps:
1) a hydrothermal process: 20mL of absolute ethyl alcohol and 15mL of isopropanol are stirred and mixed uniformly, 1mL of tetrabutyl titanate is added and stirred for 10min, the mixed solution is placed into an oven and reacts for 12 hours at a constant temperature of 180 ℃, after the reaction is finished, the precipitate is collected, centrifuged, cleaned and dried for 6 hours in vacuum at 80 ℃, and the titanium dioxide material is obtained.
2) A compounding procedure: dispersing 0.2g of the titanium dioxide material prepared in the step 1) in 50mL of deionized water, adding 1.5g of Tris (hydroxymethyl) aminomethane (Tris), adding hydrochloric acid to adjust the pH value to 10, adding 90mg of dopamine hydrochloride, reacting for 30 hours, taking out a product after the reaction is finished, centrifuging, alternately cleaning with deionized water and ethanol, and drying in vacuum at 80 ℃ for 4 hours to obtain the titanium dioxide/carbon nano material.
3) A roasting process: roasting the titanium dioxide/carbon nano material prepared in the step 2) at 800 ℃ for 7 hours in a nitrogen atmosphere, and naturally cooling to room temperature to obtain titanium dioxide/carbon particles.
4) A growth procedure: weighing 0.2g of titanium dioxide/carbon particles prepared in the step 3), dispersing in 80mL of 0.8mol/L sulfuric acid solution, adding 0.6mL of aniline, stirring in an ice bath environment, dissolving 0.8g of ammonium persulfate in 40mL of sulfuric acid, reacting for 18h, centrifuging, cleaning, and vacuum drying at 80 ℃ for 4 h to obtain the hemispherical hollow titanium dioxide/carbon particles/polyaniline.
5) A sulfuration procedure: uniformly mixing 1.0g of hemispherical hollow titanium dioxide/carbon particles/polyaniline and 5.0g of sulfur powder, putting the mixture into a polytetrafluoroethylene plastic bottle, filling argon into the bottle, keeping the temperature at 180 ℃ for 12 hours, and naturally cooling to obtain the hemispherical hollow titanium dioxide/carbon particles/polyaniline sulfur-loaded composite material.
Example 6
The composite material of titanium dioxide/carbon particles/polyaniline loaded with sulfur in a hemispherical hollow shape is applied as a positive electrode material of a lithium ion battery.
The final product titanium dioxide/carbon particles/polyaniline sulfur-loaded composite material obtained in example 3 is used as an active material of a lithium sulfur battery positive electrode, and the obtained active material, superconducting carbon black and PVDF are mixed in a ratio of 7: 2: 1, preparing uniform slurry by using an N-methyl pyrrolidone (NMP) solvent, coating the uniform slurry on an aluminum foil, putting the prepared coating in a drying oven, and drying for 4 hours at 60 ℃; after drying, moving the mixture into a vacuum drying oven, and carrying out vacuum drying for 12 hours at the temperature of 60 ℃; and tabletting and cutting the dried composite material coating by a tablet press and the like.
The lithium sheet is used as a counter electrode, 1M LiTFSI/DME + DOL solution is used as electrolyte, the battery is installed in an argon atmosphere, finally, a battery tester is used for testing the charge and discharge performance, and the obtained product is used as the anode material of the lithium-sulfur battery, and the cycle stability test result under the current density of 0.1C is shown in the attached figure 9. As can be seen from FIG. 9, the cycling stability of the battery is good, and the battery is cycled for 50 timesThe capacity is still higher than 1200mAh g-1。
The above detailed description of the hemispherical hollow titanium dioxide/carbon particle/polyaniline sulfur-loaded composite material, the preparation method thereof, the lithium sulfur battery positive electrode and the battery, which are described with reference to the examples, is illustrative and not restrictive, and several examples can be cited within the limits thereof, so that variations and modifications thereof without departing from the general concept of the present invention should fall within the scope of the present invention.

Claims (10)

1. A preparation method of a semispherical hollow titanium dioxide/carbon particle/polyaniline sulfur-loaded composite material is characterized by comprising the following steps:
1) uniformly mixing absolute ethyl alcohol and isopropanol, adding tetrabutyl titanate, uniformly mixing, and carrying out hydrothermal reaction to obtain a titanium dioxide material;
2) dispersing the titanium dioxide material prepared in the step 1) in water, adding trihydroxymethyl aminomethane, adding dopamine hydrochloride, reacting, and obtaining a titanium dioxide/carbon nano material after the reaction is finished;
3) roasting the titanium dioxide/carbon nano material prepared in the step 2) in a nitrogen atmosphere, and naturally cooling to room temperature to prepare titanium dioxide/carbon particles;
4) dispersing the titanium dioxide/carbon particles prepared in the step 3) in a sulfuric acid solution under an ice bath condition, adding aniline, uniformly stirring, and then adding ammonium persulfate to react to obtain hemispherical hollow titanium dioxide/carbon particles/polyaniline;
5) uniformly mixing the hemispherical hollow titanium dioxide/carbon particles/polyaniline prepared in the step 4) with sulfur powder, and fumigating sulfur in an argon atmosphere to obtain a hemispherical hollow titanium dioxide/carbon particles/polyaniline sulfur-loaded composite material;
the step 2) also comprises the following steps: and adding trihydroxymethyl aminomethane to adjust the pH of the system to 6.5-10.
2. The preparation method according to claim 1, wherein in step 1), the volume ratio of the absolute ethyl alcohol to the isopropyl alcohol to the tetrabutyl titanate is (10-30): (10-20): (0.1 to 1.0); the hydrothermal reaction condition is 150-200 ℃ for 4-12 h.
3. The preparation method according to claim 1, wherein in the step 2), the mass ratio of the titanium dioxide material, the tris (hydroxymethyl) aminomethane and the dopamine hydrochloride is 1: (1-8): (0.2 to 0.5); the concentration of the titanium dioxide material in water is 2-6 g/L.
4. The preparation method according to claim 1, wherein in the step 2), the reaction time is 18-30 h.
5. The preparation method of claim 1, wherein in the step 3), the roasting condition is 500-800 ℃ for 2-8 h.
6. The method according to claim 1, wherein in step 4), the ratio of the titanium dioxide/carbon particles to the aniline to the ammonium persulfate is 1 g: (0.15-3.0) mL (2-4) g; the concentration of the titanium dioxide/carbon particles in sulfuric acid is 2-6 g/L; the concentration of the sulfuric acid is 0.3-1 mol/L.
7. The preparation method according to claim 1, wherein in the step 5), the mass ratio of the hemispherical hollow titanium dioxide/carbon particles/polyaniline to the sulfur powder is 1: 1-5; the sulfuring condition is 140-180 ℃ sulfuring for 12-18 h.
8. The application of the semispherical hollow titanium dioxide/carbon particle/polyaniline sulfur-loaded composite material prepared by the preparation method of any one of claims 1 to 7 as a lithium ion battery positive electrode material.
9. A positive electrode for a lithium-sulfur battery, characterized by being made of the semispherical hollow titanium dioxide/carbon particle/polyaniline sulfur-loaded composite material prepared by the preparation method of any one of claims 1 to 7.
10. A battery comprising the lithium sulfur battery positive electrode of claim 9.
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